Pesticidally active O-alkyl-O-[6-tert.-butyl-pyrimidin(4)yl]-(thiono)(thiol)-phosphoric(phosphonic) acid esters

ABSTRACT

O-Alkyl-O-[6-tert.-butyl-pyrimidin(4)yl](thiono)(thiol)-phosphoric(phosphonic) acid esters of the formula ##STR1## in which R is hydrogen, halogen or alkyl, 
     R 1  is hydrogen or alkyl, 
     R 2  is alkyl, 
     R 3  is alkyl, alkoxy, alkylthio or phenyl, and 
     X is oxygen or sulphur. which possess insecticidal and acaricidal properties.

The present invention relates to and has for its objects the provisionof particular newO-alkyl-O-[6-tert.-butylpyrimidin(4)yl]-(thiono)(thiol)-phosphoric(phosphonic)acid esters which possess insecticidal and acaricidal properties, activecompositions in the form of mixtures of such compounds with solid andliquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating pests, e.g. insects and acarids, with other and furtherobjects becoming apparent from a study of the within specification andaccompanying examples.

It is known from U.S. Pat. Nos. 3,216,894 and 3,886,156 that certainmethyl-substituted pyrimidinylthionophosphoric(phosphonic) acid esters,for example O-methyl- andO-ethyl-O-[2,6-dimethyl-pyrimidin(4)-yl]-ethane- and-methane-thionophosphonic acid esters andO,O-diethyl-O-[2,5-dimethylthio-6-methylpyrimidin(4)yl]-thionophosphoricacid ester, possess insecticidal and acaricidal properties.

The present invention now provides, as new compounds, thepyrimidinyl(thiono)(thiol)-phosphoric(phosphonic) acid esters of thegeneral formula ##STR2## in which

R is hydrogen, halogen or alkyl,

R¹ is hydrogen or alkyl,

R² is alkyl,

R³ is alkyl, alkoxy, alkylthio or phenyl, and

X is oxygen or sulphur.

Preferably, R represents hydrogen or chlorine, R¹ represents hydrogen orstraight-chain or branched alkyl with 1 to 6 (especially 1 to 4) carbonatoms, R² represents straight-chain or branched alkyl with 1 to 6(especially 1 to 4) carbon atoms, R³ represents straight-chain orbranched alkoxy or alkylthio each with 1 to 6 (especially with 1 to 4)carbon atoms or straight-chain or branched alkyl with 1 to 8 (especially1 to 5) carbon atoms, or phenyl and X represents sulphur. In a preferredsub-group R² is ethyl while R³ is S-n-propyl.

Surprisingly, the pyrimidinyl(thiono)(thiol)-phosphoric(phosphonic acidesters according to the invention exhibit a better insecticidal andacaricidal action than the known methyl-substitutedpyrimidinylthionophosphoric(phosphonic) acid esters of analogousstructure and of the same type of action. The compounds according to thepresent invention thus represent a genuine enrichment of the art.

The invention also provides a process for the preparation of apyrimidinyl(thiono)(thiol)-phosphoric (phosphonic) acid ester of theformula (I) in which a (thiono)(thiol)-phosphoric(phosphonic) acid esterhalide of the general formula ##STR3## in which

R², R³ and X have the above-mentioned meanings and

Hal represents halogen, preferably chlorine, is reacted, if appropriatein the presence of a solvent or diluent, with a4-hydroxy-6-tert.-butyl-pyrimidine of the formula ##STR4## in which

R and R¹ have the above-mentioned meaning, the latter being employed assuch in the presence of an acid acceptor or in the form of an alkalimetal salt, alkaline earth metal salt or ammonium salt.

If, for example, O-sec.-butyl-ethane-thiono-phosphonic acid esterchloride and 2-n-propyl-4-hydroxy-5-methyl-6-tert.-butyl-pyrimidine areused as starting materials, the course of the reaction can berepresented by the following equation: ##STR5##

The (thiono)(thiol)-phosphoric(phosphonic) acid ester halides (II) to beused as starting materials are known and can readily be prepared, evenon an industrial scale, in accordance with processes known from theliterature. The following may be mentioned as individual examplesthereof: O,O-dimethyl-, O,O-diethyl-, O,O-di-n-propyl-,O,O-di-isopropyl-, O,O-di-n-butyl-, O,O-di-iso-butyl-,O,O-di-sec.-butyl-, O-methyl-O-ethyl-, O-methyl-O-n-propyl-,O-methyl-O-iso-propyl-, O-methyl-O-n-butyl, O-methyl-O-isobutyl-,O-methyl-O-sec.-butyl-, O-ethyl-O-n-propyl-, O-ethyl-O-iso-propyl-,O-ethyl-O-n-butyl-, O-ethyl-O-sec.butyl-, O-ethyl-O-iso-butyl-,O-n-propyl-O-butyl- and O-iso-propyl-O-butyl-thionophosphoric aciddiester chloride, as well as O,S-dimethyl-, O,S-diethyl-,O,S-di-n-propyl-, O,S-di-isopropyl-, O,S-di-n-butyl-, O,S-di-iso-butyl-,O-ethyl-S-n-propyl-, O-ethyl-S-iso-propyl-, O-ethyl-S-n-butyl-,O-ethyl-S-sec.-butyl-, O-n-propyl-S-ethyl-, O-n-propyl-S-iso-propyl,O-n-butyl-S-n-propyl- and O-sec.-butyl-S-ethylthionothiolphosphoric aciddiester chloride and O-methyl-, O-ethyl-, O-n-propyl-, O-iso-propyl-,O-n-butyl-, O-iso-butyl- and O-sec.-butyl-methane-, ethane-, n-propane-,iso-propane-, n-butane-, iso-butane-, tert.-butane-, sec.-butane-,n-pentane- and benzene-thionophosphonic acid ester chloride.

The 4-hydroxy-6-tert.-butyl-pyrimidines (III), also to be used asstarting materials, can also be prepared in accordance with processesknown from the literature, for example by condensing acylamidinehydrochlorides with pivaloylacetic acid alkyl ester derivatives, ifappropriate in the presence of an alcoholate. The following may bementioned as individual examples thereof: 6-tert.-butyl- and5-chloro-6-tert.-butyl-4-hydroxy-pyrimidine, as well as 2-methyl-,2-ethyl-, 2-n-propyl-, 2-iso-propyl-, 2-n-butyl-, 2-sec.-butyl-,2-iso-butyl-, 2-tert.-butyl-, 2-methyl-5-chloro-, 2-ethyl-5-chloro-,2-n-propyl-5-chloro-, 2-iso-propyl-5-chloro-, 2-n-butyl-5-chloro-,2-iso-butyl-5-chloro- and2-sec.-butyl-5-chloro-4-hydroxy-6-tert.-butyl-pyrimidine.

The process for the preparation of the compounds according to theinvention is preferably carried out in the presence of a suitablesolvent or diluent. Virtually all inert organic solvents can be used forthis purpose, especially aliphatic and aromatic, optionally chlorinated,hydrocarbons, such as benzene, toluene, xylene, benzine, methylenechloride, chloroform, carbon tetrachloride and chlorobenzene; ethers,for example diethyl ether, dibutyl ether and dioxane, ketones, forexample acetone, methyl ethyl ketone, methyl isopropyl ketone and methylisobutyl ketone; and nitriles; such as acetonitrile and propionitrile.

All customary acid-binding agents can be used as acid acceptors. Alkalimetal carbonates and alkali metal alcoholates, such as sodium carbonateand potassium carbonate, sodium methylate and ethylate and potassiummethylate, ethylate and tert.-butylate, have proved particularlysuitable, as have aliphatic, aromatic or heterocyclic amines, forexample triethylamine, trimethylamine, dimethylaniline,dimethylbenzylamine and pyridine.

The reaction temperature can be varied within a fairly wide range. Ingeneral, the reaction is carried out at from 0° to 120° C. preferably atfrom 20° to 60° C.

In general, the reaction is allowed to take place under normal pressure.

To carry out the process, the starting materials are preferably employedin equimolar amounts. An excess of one or other reactant produces nosignificant advantages.

In general, the reactants are combined in one of the stated solvents andare stirred for one or more hours, in most cases at an elevatedtemperature, to complete the reaction. After cooling, an organicsolvent, for example toluene, is added to the mixture and the organicphase is worked up in the usual manner by washing, drying, anddistilling off the solvent.

The new compounds are frequently obtained in the form of oils, which inmost cases cannot be distilled without decomposition, but are freed fromthe last volatile constituents by so-called "slight distillation", thatis to say by prolonged heating under reduced pressure to moderatelyelevated temperatures, and are purified in this way. They arecharacterized by the refractive index.

As already mentioned, the compounds according to the present inventionare distinguished by an excellent insecticidal and acaricidal activity.They are therefore active against plant pests, pests harmful to healthand pests of stored products and combine a low phytotoxicity with a goodaction against sucking and biting insects and against mites.

For this reason, the compounds according to the invention can beemployed successfully as pesticides in plant protection and in thehygiene field and the field of protection of stored products.

The compounds according to the present invention can also be used in thefield of veterinary medicine, since they are also active against animalparasites, in particular ectoparasites such as parasitic fly larvae.

The active compounds are well tolerated by plants, have a favorablelevel of toxicity to warm-blooded animals, and can be used for combatingarthropod pests, especially insects and acarids, and nematode pestswhich are encountered in agriculture, in forestry, in the protection ofstored products and of materials, and in the hygiene field. They areactive against normally sensitive and resistant species and against allor some stages of development. The abovementioned pests include:

from the class of the Isopoda, for example Oniscus asellus,Armadillidium vulgare and Porcellio scaber;

from the class of the Diplopoda, for example Blaniulus guttulatus;

from the class of the Chilopoda, for example Geophilus carpophagus andScutigera spec.;

from the class of the Symphyla, for example Scutigerella immaculata;

from the order of the Thysanura, for example Lepisma saccharina;

from the order of the Collembola, for example Onychiurus armatus;

from the order of the Orthoptera, for example Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria;

from the order of the Dermaptera, for example Forficula auricularia;

from the order of the Isoptera, for example Reticulitermes spp.;

from the order of the Anoplura, for example Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.;

from the order of the Mallophaga, for example Trichodectes spp. andDamalinea spp.;

from the order of the Thysanoptera, for example Hercinothrips femoralisand Thrips tabaci;

from the order of the Heteroptera, for example Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.;

from the order of the Homoptera, for example Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.;

from the order of the Lepidoptera, for example Pectinophora gossypiella,Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella,Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria,Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella,Pyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Eariasinsulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolisflammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsapomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestiakuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana,Choristoneura fumiferana, Clysia ambiguella, Homona magnanima andTortrix viridana;

from the order of the Coleoptera, for example Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica;

from the order of the Hymenoptera, for example Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.;

from the order of the Diptera, for example Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa;

from the order of the Siphonaptera, for example Xenopsylla cheopis andCeratophyllus spp.;

from the class of the Arachnida, for example Scorpio maurus andLatrodectus mactans;

from the order of the Acarina, for example Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoriptes spp., Chlorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychusspp..

The plant-parasitic nematodes include Pratylenchus spp., Radopholussimilis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heteroderaspp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinemaspp., and Trichodorus spp..

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual activity on woodand clay as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents, carriers or extenders ofthe type usable in conventional pesticide formulations or compositions,e.g. conventional pesticide dispersible carrier vehicles such as gases,solutions, emulsions, wettable powders, suspensions, powders, dustingagents, foams, pastes, soluble powders, granules, aerosols,suspension-emulsion concentrates, seed-treatment powders, natural andsynthetic materials impregnated with active compound, very fine capsulesin polymeric substances and in coating compositions, for use on seed,and formulations used with burning equipment, such as fumigatingcartridges, fumigating cans, fumigating coils and the like, as well asULV cold mist and warm mist formulations.

These are prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticide surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: aerosol propellants which are gaseous at normal temperaturesand pressures, such as halogenated hydrocarbons, e.g.dichlorodifluoromethane and trichlorofluoromethane, as well as butane,propane, nitrogen and carbon dioxide; inert dispersible liquid diluentcarriers, including inert organic solvents, such as aromatichydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.),halogenated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), cycloalkanes, (e.g. cyclohexane), etc.),paraffins (e.g. petroleum or mineral oil fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.),alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) aswell as ethers and esters thereof (e.g. glycol monomethyl ether, etc.),amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide,etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones(e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone,cyclohexanone, etc.), and/or water; as solid carriers, ground naturalminerals, such as kaolins, clays, talc, chalk, quartz, attapulgite,montmorillonite or diatomaceous earth, and ground synthetic minerals,such as highly-dispersed silicic acid, alumina and silicates; as solidcarriers for granules; crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, as well as syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, corn cobs and tobacco stalks;whereas the following may be chiefly considered for use as conventionalcarrier vehicle assistants, e.g. surface-active agents, for thispurpose: emulsifying agents, such as non-ionic and/or anionicemulsifying agents (e.g. polyethylene oxide esters of fatty acids,polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkylsulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especiallyalkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.);and/or dispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulations.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other arthropodicides, ornematicides, fungicides, bactericides, rodenticides, herbicides,fertilizers, growth-regulating agents, etc., if desired, or in the formof particular dosage preparations for specific application madetherefrom, such as solutions, emulsions, suspensions, powders, pastes,and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.1-95% by weight, andpreferably 0.5-90% by weight, of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.0000001-100,preferably 0.01-10%, by weight of the mixture. Thus, the presentinvention contemplates overall compositions which comprise mixtures of aconventional dispersible carrier such as (1) a dispersible inert finelydivided carrier solid, and/or (2) a dispersible carrier liquid such asan inert organic solvent and/or water, preferably including asurface-active effective amount of a carrier vehicle assistant, e.g. asurface-active agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active compound which is effective for thepurpose in question and which is generally between about 0.0001-95%, andpreferably 0.01-95%, by weight of the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 15 to 1000 g/hectare, preferably 40to 600 g/hectare, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of the activecompound or even the 100% active substance alone, e.g. about 20-100% byweight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects and acarids, whichcomprises applying to at least one of correspondingly (a) such insects,(b) such acarids, and (c) the corresponding habitat thereof, i.e. thelocus to be protected, e.g. to a growing crop, to an area where a cropis to be grown or to a domestic animal, a correspondingly combative ortoxic amount, i.e. an insecticidally or acaricidally effective amount,of the particular active compound of the invention alone or togetherwith a carrier vehicle as noted above. The instant formulations orcompositions are applied in the usual manner, for instance by spraying,atomizing, vaporizing, scattering, dusting, watering, squirting,sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

EXAMPLE 1

The 4-hydroxy-6-tert.-butyl-pyrimidines (III) required as startingmaterials could be prepared, for example, as described below: ##STR6##

A suspension of 21.6 g (0.4 mol) of sodium methylate, 19.4 g (0.2 mol)of acetamidine hydrochloride, 34.4 g (0.2 mol) of pivaloylacetic acidethyl ester and 100 ml of methanol was heated for 10 hours under refluxand then evaporated, and the residue was taken up in 350 ml of water.Concentrated hydrochloric acid was added to the aqueous solution, whilecooling with ice, to a pH of about 6, and the mixture was then extractedtwice with 200 ml of methylene chloride each time. The combinedmethylene chloride extracts were dried over sodium sulphate and thenconcentrated. 21 g (63% of theory) of2-methyl-4-hydroxy-6-tert.-butyl-pyrimidine were obtained in the form ofcolorless crystals of melting point 131°-132° C.

The following compounds of the formula ##STR7## could be preparedanalogously:

                  TABLE 1                                                         ______________________________________                                                             Yield      Melting                                                            (% of      point,                                        R      R.sup.1       theory)    °C.                                    ______________________________________                                        H      C.sub.2 H.sub.5                                                                             79          46                                           H      H             45         218                                           H      C.sub.3 H.sub.7 -iso                                                                        62         113                                           ______________________________________                                    

EXAMPLE 2 ##STR8##

18.8 g (0.1 mol) of O,O-diethylthionophosphoric acid diester chloridewere added dropwise to a mixture of 16.6 g (0.1 mol) of2-methyl-4-hydroxy-6-tert.-butyl-pyrimidine, 14.5 g (0.105 mol) ofpotassium carbonate and 200 ml of acetonitrile. The batch was warmed to40° C. for 3 hours and was then cooled, and the reaction mixture waspoured into 300 ml of toluene. The toluene solution was washed withsaturated sodium bicarbonate solution and water, dried over sodiumsulphate and concentrated. After slight distillation, 22 g (69% oftheory) ofO,O-diethyl-O-[2-methyl-6-tert.-butyl-pyrimidin(4)yl]-thionophosphoricacid ester were obtained in the form of a yellow oil having a refractiveindex n_(D) ²³ of 1.4930.

The following compounds of the formula ##STR9## could be synthesizedanalogously:

                                      TABLE 2                                     __________________________________________________________________________                                Yield                                             Compound                    (% of                                                                              Refractive                                   No.   R R.sup.1                                                                             R.sup.2                                                                             R.sup.3                                                                             X theory)                                                                            index:                                       __________________________________________________________________________    2     H CH.sub.3                                                                            C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     S 70   n.sub.D.sup.23 :1.5060                       3     H CH.sub.3                                                                            C.sub.2 H.sub.5                                                                     CH.sub.3                                                                            S 74   n.sub.D.sup.23 :1.5090                       4     H CH.sub.3                                                                            C.sub.3 H.sub.7 -iso                                                                CH.sub.3                                                                            S 70   n.sub.D.sup.23 :1.5035                       5     H CH.sub.3                                                                            C.sub.3 H.sub.7 -n                                                                  OCH.sub.3                                                                           S 54   n.sub.D.sup.23 :1.4968                       6     H CH.sub.3                                                                            CH.sub.3                                                                            OCH.sub.3                                                                           S 40   n.sub.D.sup.23 :1.5048                       7     H CH.sub.3                                                                            C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                    O 51   n.sub.D.sup.23 :1.4679                       8     H CH.sub.3                                                                            C.sub.2 H.sub.5                                                                      ##STR10##                                                                          S 81   n.sub.D.sup.22 :1.5540                       9     H C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                    S 64   n.sub.D.sup.23 :1.4873                       10    H C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     S 76   n.sub.D.sup.23 :1.4977                       11    H C.sub.2 H.sub.5                                                                     CH.sub.3                                                                            OCH.sub.3                                                                           S 39   n.sub.D.sup.23 :1.4909                       12    H C.sub.2 H.sub.5                                                                     C.sub.3 H.sub.7 -iso                                                                CH.sub.3                                                                            S 76   n.sub.D.sup.23 :1.4948                       13    H C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     SC.sub.3 H.sub.7 -n                                                                 S 66   n.sub.D.sup.23 :1.5186                       14    H C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                      ##STR11##                                                                          S 73   n.sub.D.sup.23 :1.5404                       15    H C.sub.2 H.sub.5                                                                     CH.sub.3                                                                            C.sub.2 H.sub.5                                                                     S 71   n.sub.D.sup.23 :1.5048                       16    H C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                    O 72   n.sub.D.sup.23 :1.4538                       17    H H     C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                    O 78   n.sub.D.sup.23 :1.4709                       18    H H     C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                    S 74   n.sub.D.sup.23 :1.4950                       19    H H     CH.sub.3                                                                            OCH.sub.3                                                                           S 54   n.sub.D.sup.23 :1.5072                       20    H H     C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     S 87   n.sub.D.sup.23 :1.5123                       21    H H     C.sub.2 H.sub.5                                                                     SC.sub.3 H.sub.7 -n                                                                 S 71   n.sub. D.sup.23 :1.5268                      22    H H     C.sub.3 H.sub.7 -iso                                                                CH.sub.3                                                                            S 78   n.sub.D.sup.23 :1.5110                       23    H H     C.sub.2 H.sub.5                                                                     CH.sub.3                                                                            S 73   n.sub.D.sup.23 :1.5150                       24    H H     C.sub.2 H.sub.5                                                                      ##STR12##                                                                          S 70   n.sub.D.sup.23 :1.5581                       25    H H     CH.sub.3                                                                            C.sub.2 H.sub.5                                                                     S 82   n.sub.A.sup.23 :1.5199                       26    H H     C.sub.2 H.sub.5                                                                     C.sub.4 H.sub.9 -sec.                                                               S 90   n.sub.D.sup.23 :1.5102                       27    H H     CH.sub.3                                                                            OC.sub.3 H.sub.7 -n                                                                 S 59   n.sub.D.sup.23 :1.5321                       28    Cl                                                                              H     C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                    S 89   n.sub.D.sup.23 :1.5061                       29    Cl                                                                              H     C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     S 84   n.sub.D.sup.23 :1.5169                       30    Cl                                                                              H     C.sub.2 H.sub.5                                                                      ##STR13##                                                                          S 76   n.sub.D.sup.23 :1.5611                       31    Cl                                                                              H     CH.sub.3                                                                            OC.sub.3 H.sub.7 -n                                                                 S 80   n.sub.D.sup.23 :1.5080                       32    Cl                                                                              H     C.sub.2 H.sub.5                                                                     OC.sub.3 H.sub.7 -n                                                                 S 81   103° C. (m.pt)                        33    H C.sub.3 H.sub.7 -iso                                                                C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                    S 95   n.sub.D.sup.23 :1.4880                       34    H C.sub.3 H.sub.7 -iso                                                                C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     S 85   n.sub.D.sup.23 :1.4967                       35    H C.sub.3 H.sub.7 -iso                                                                C.sub.2 H.sub.5                                                                     SC.sub.3 H.sub.7 -n                                                                 S 90   n.sub.D.sup.23 :1.5130                       36    H C.sub.3 H.sub.7 -iso                                                                CH.sub.3                                                                            OCH.sub.3                                                                           S 78   n.sub.D.sup.23 :1.4960                       37    H C.sub.3 H.sub.7 -iso                                                                C.sub.3 H.sub.7 -iso                                                                CH.sub.3                                                                            S 82   n.sub.D.sup.23 :1.4940                       38    H C.sub.3 H.sub.7 -iso                                                                C.sub.2 H.sub.5                                                                      ##STR14##                                                                          S 74   n.sub.D.sup.23 :1.5380                       39    H C.sub.3 H.sub.7 -iso                                                                C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                    O 76   n.sub.D.sup.23 :1.4660                       40    H C.sub.3 H.sub.7 -iso                                                                C.sub.2 H.sub.5                                                                     CH.sub.3                                                                            S 79   n.sub.D.sup.23 :1.4983                       41    H C.sub.3 H.sub.7 -iso                                                                CH.sub.3                                                                            C.sub.2 H.sub.5                                                                     S 88   n.sub.D.sup.23 :1.5024                       42    H C.sub.3 H.sub.7 -iso                                                                C.sub.2 H.sub.5                                                                     C.sub.4 H.sub.9 -sec.                                                               S 89   n.sub.D.sup.23 :1.4984                       43    H C.sub.3 H.sub. 7 -iso                                                               C.sub.2 H.sub.5                                                                     OC.sub.3 H.sub.7 -n                                                                 S 95   n.sub.D.sup.23 :1.4865                       44    H C.sub.5 H.sub.11 -n                                                                 CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                    S                                                   45    H H     C.sub.5 H.sub.11 -sec.                                                              OC.sub.2 H.sub.5                                                                    S                                                   46    H H     CH.sub.3                                                                            OC.sub.5 H.sub.11 -n                                                                S                                                   47    H H     CH.sub.3                                                                            SC.sub.4 H.sub.9 -n                                                                 S                                                   __________________________________________________________________________

the activity of the compounds of this invention is illustrated by thefollowing biotest examples in which the compounds according to thepresent invention are each identified by the number (given in brackets)from the preparative examples hereinabove.

The known comparison compounds are identified as follows:

    ______________________________________                                        (A) =                                                                                         ##STR15##                                                     (B) =                                                                                         ##STR16##                                                     (C) =                                                                                         ##STR17##                                                     (D) =                                                                                         ##STR18##                                                     ______________________________________                                    

example 3

lt₁₀₀ test for Diptera

Test insects: Aedes aegypti

Solvent: Acetone

The active compound was dissolved in the solvent at a rate of 2 g perliter. The solution so obtained was diluted with further solvent to thedesired lower concentrations.

2.5 ml of the solution of active compound were pipetted into a Petridish. On the bottom of the Petri dish there was a filter paper with adiameter of about 9.5 cm. The Petri dish remained uncovered until thesolvent had completely evaporated. The amount of active compound persquare meter of filter paper varied with the concentration of thesolution of active compound. About 25 test insects were then placed inthe Petri dish and it was covered with a glass lid.

The condition of the test insects was continuously observed. The timewhich was necessary for 100% destruction was determined.

The active compounds, the concentrations of the active compounds and thetimes at which there was 100% destruction can be seen from the followingtable:

                  Table 3                                                         ______________________________________                                        (LT.sub.100 test for Diptera/Aedes aegypti)                                                 Active compound LT.sub.100 in                                                 concentration of                                                                              minutes                                                       the solution,   (') or                                          Active compound                                                                             in %            hours (h)                                       ______________________________________                                        (A)           0.02            3.sup.h = 0                                     (11)          0.02            180'                                            (16)          0.02            120'                                            (4)           0.02            120'                                            (17)          0.02            120'                                            (22)          0.02            60'                                             (23)          0.02            60'                                             (25)          0.02            120'                                            (1)           0.02            60'                                             ______________________________________                                    

EXAMPLE 4

Mosquito larvae test

Test insects: Aedes aegypti larvae

Solvent: 99 parts by weight of acetone

Emulsifier: 1 part by weight of benzylhydroxydiphenyl polyglycol ether

To produce a suitable preparation, the active compound was dissolved, ata rate of 2 g per liter, in the solvent containing the amount ofemulsifier stated above. The solution thus obtained was diluted withwater to the desired lower concentrations.

The aqueous preparations of the active compounds were placed in glassvessels and about 25 mosquito larvae were then placed in each glassvessel.

After 24 hours, the degree of destruction was determined as apercentage. 100% meant that all of the larvae were killed. 0% meant thatnone of the larvae were killed.

The active compounds, the concentrations of the active compounds and theresults can be seen from the following table:

                  Table 4                                                         ______________________________________                                        (Mosquito larvae test/Aedes aegypti)                                                        Active com-                                                                   pound con-                                                                    centration    Degree of                                                       of the solu-  destruction                                       Active compound                                                                             tion, in ppm  in %                                              ______________________________________                                        (B)           1             0                                                 (C)           1             0                                                 (D)           1             0                                                 (9)           1             95                                                (10)          1             100                                               (13)          1             100                                               (14)          1             90                                                (2)           1             100                                               (3)           1             100                                               (5)           1             100                                               (6)           1             90                                                (18)          1             100                                               (19)          1             100                                               (20)          1             100                                               (21)          1             100                                               (24)          1             100                                               (27)          1             100                                               ______________________________________                                    

EXAMPLE 5

Plutella test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof the active compound was mixed with the stated amount of solventcontaining the stated amount of emulsifier and the concentrate wasdiluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) were sprayed with the preparation ofthe active compound until dew moist and were then infested withcaterpillars of the diamond-back moth (Plutella maculipennis).

After the specified periods of time, the degree of destruction wasdetermined as a percentage: 100% meant that all of the caterpillars werekilled whereas 0% meant that none of the caterpillars were killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following table:

                  Table 5                                                         ______________________________________                                        (Plutella test)                                                                             Active com-   Degree of                                                       pound con-    destruction                                                     centration in in % after                                        Active compound                                                                             %             3 days                                            ______________________________________                                        (A)           0.1           80                                                              0.01          0                                                 (19)          0.1           100                                                             0.01          100                                               (6)           0.1           100                                                             0.01          100                                               (18)          0.1           100                                                             0.01          100                                               (17)          0.1           100                                                             0.01          100                                               (1)           0.1           100                                                             0.01          100                                               (7)           0.1           100                                                             0.01          100                                               (9)           0.1           100                                                             0.01          100                                               (3)           0.1           100                                                             0.01          100                                               (25)          0.1           100                                                             0.01          100                                               (15)          0.1           100                                                             0.01          100                                               (20)          0.1           100                                                             0.01          100                                               (2)           0.1           100                                                             0.01          100                                               (10)          0.1           100                                                             0.01          100                                               (34)          0.1           100                                                             0.01          100                                               (27)          0.1           100                                                             0.01          100                                               (5)           0.1           100                                                             0.01          100                                               (22)          0.1           100                                                             0.01          100                                               (4)           0.1           100                                                             0.01          100                                               (12)          0.1           100                                                             0.01          100                                               (37)          0.1           100                                                             0.01          100                                               (21)          0.1           100                                                             0.01          100                                               (13)          0.1           100                                                             0.01          100                                               (35)          0.1           100                                                             0.01          100                                               (24)          0.1           100                                                             0.01          100                                               (8)           0.1           100                                                             0.01          100                                               (14)          0.1           100                                                             0.01          100                                               ______________________________________                                    

EXAMPLE 6

Tetranychus test (resistant)

Solvent: 3 parts by weight of dimethylformamide

Emuslifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof the active compound was mixed with the stated amount of solvent andthe stated amount of emulsifier and the concentrate was diluted withwater to the desired concentration.

Bean plants (Phaseolus vulgaris) which were heavily infested with thetwo-spotted spider mite (Tetranychus urticae) in all stages ofdevelopment were sprayed with the preparation of the active compounduntil dripping wet.

After the specified periods of time, the degree of destruction wasdetermined as a percentage: 100% meant that all of the spider mites werekilled whereas 0% meant that none of the spider mites were killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following table:

    ______________________________________                                        (Tetranychus test/resistant)                                                                Active com-   Degree of                                                       pound con-    destruction                                                     centration    in % after                                        Active compound                                                                             in %          2 days                                            ______________________________________                                        (A)           0.1           100                                               (39)          0.1           99                                                (23)          0.1           100                                               (3)           0.1           100                                               (22)          0.1           100                                               (35)          0.1           100                                               ______________________________________                                    

EXAMPLE 7

Test insect: Phorbia antiqua grubs in the soil

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amount of solvent, thestated amount of emulsifier was added and the concentrate was dilutedwith water to the desired concentration.

The amount of active compound was intimately mixed with the soil. Theconcentration of the active compound in the preparation was practicallyimmaterial, the only decisive factor being the amount by weight ofactive compound per unit volume of soil, which is quoted hereinafter inppm (=mg/l). The treated soil was filled into pots and the pots wereleft to stand at room temperature.

After 24 hours the test insects were introduced into the treated soiland after a further 2 to 7 days the degree of effectiveness of theactive compound was determined in % by counting the dead and the livetest insects. The degree of effectiveness was 100% if all of the testinsects had been killed and was 0% if exactly as many test insects werestill alive as in the case of the untreated control.

The active compounds, the amounts used and the results can be seen fromthe table which follows:

                  Table 7                                                         ______________________________________                                        (Phorbia antiqua grubs in the soil)                                                           Degree of destruction                                                         in % at an active com-                                                        pound concentration of                                        Active compound 10 ppm                                                        ______________________________________                                        (A)             0                                                             (B)             0                                                             (9)             100                                                           (11)            100                                                           (12)            100                                                           (15)            100                                                           (1)             100                                                           (33)            100                                                           (34)            100                                                           (35)            100                                                           (36)            100                                                           (37)            100                                                           (38)            100                                                           (40)            100                                                           (41)            100                                                           (43)            100                                                           ______________________________________                                    

EXAMPLE 8

Test insect: Tenebrio molitor larvae in the soil

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amount of solvent, thestated amount of emulsifier was added and the concentrate was dilutedwith water to the desired concentration.

The amount of active compound was intimately mixed with the soil. Theconcentration of the active compound in the preparation was practicallyimmaterial, the only decisive factor being the amount by weight ofactive compound per unit volume of soil, which is quoted hereinafter inppm (=mg/l). The treated soil was filled into pots and the pots wereleft to stand at room temperature.

After 24 hours the test insects were introduced in to the treated soiland after a further 2 to 7 days the degree of effectiveness of theactive compound was determined in % by counting the dead and the livetest insects. The degree of effectiveness was 100% if all of the testinsects had been killed and was 0% if exactly as many test insects werestill alive as in the case of the untreated control.

The active compounds, the amounts used and the results can be seen fromthe table which follows:

                  Table 8                                                         ______________________________________                                        (Tenebrio molitor larvae in the soil)                                                         Degree of destruction                                                         in % at an active com-                                                        pound concentration of                                        Active compound 5 ppm                                                         ______________________________________                                        (A)             0                                                             (B)             0                                                             (20)            100                                                           (18)            100                                                           (25)            100                                                           (26)            100                                                           (27)            100                                                           ______________________________________                                    

EXAMPLE 9

Test on blowfly larvae

Screening test on Lucilia cuprina/tube in vitro

Test animal: Freshly hatched, about 12-24 hours old, sensitive blowflylarvae (Lucilia cuprina).

Test method: About 20-30 larvae per concentration were introduced into aseries of preparations (100, 10 and 1 ppm). For this purpose, larvaewere placed on cottonwool plugs (diameter 1.7 cm, height 1 cm, MessrsRescheisen u. Co., Ulm) contained in glass tubes (white diffusing tubes,43/44×23/24 mm, made from Bunder glass, Article No. 7,301,009), theplugs having beforehand been moistened with 2.5 ml of a 25% strengthsuspension of bonemeal in water.

0.5 ml of the preparation to be tested was then pipetted onto thesemoistened cottonwool plugs. The tubes were then transferred to, and keptin, a climatically controlled room (27°±1° C., humidity±5%). The actionwas examined after 24 hours.

Test criteria: The criterion of the action was the occurrence of deathof the treated larvae.

The active compounds, active compound concentrations and results can beseen from the table which follows:

                  Table 9                                                         ______________________________________                                        (Test on blowfly larvae (Lucilia cuprina))                                                  Active com-                                                                   pound con-    Degree of                                                       centration    destruction                                       Active compound                                                                             in ppm        in %                                              ______________________________________                                        (34)          100           100                                                             30            100                                                             10            100                                               (36)          100           100                                                             30            100                                                             10            100                                                             3             100                                               (40)          100           100                                                             10            100                                               (41)          100           100                                                             30            100                                                             10            100                                                             3             >50                                                             1             >50                                               ______________________________________                                    

It will be appreciated that the instant specification and claims are setforth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. AnO-alkyl-O-[6-tert.-butylpyrimidin(4)yl](thiono)(thiol)-phosphoric(phosphonic)acid ester of the formula ##STR19## in which R is hydrogen, halogen oralkyl,R¹ is hydrogen or alkyl, R² is alkyl, R³ is alkyl, alkoxy,alkylthio or phenyl, and X is oxygen or sulphur, the various alkylmoieties having 1 to 6 carbon atoms.
 2. A compound according to claim 1,in whichR is hydrogen or chlorine, R³ is alkoxy or alkylthio each with 1to 6 carbon atoms, or phenyl, and X is sulphur.
 3. A compound accordingto claim 1, wherein the compound isO,O-diethyl-O-[2-methyl-6-tert.-butyl-pyrimidin(4)yl]-thionophosphoricacid ester of the formula ##STR20##
 4. A compound according to claim 1,wherein the compound isO,O-dimethyl-O-[2-methyl-6-tert.-butyl-pyrimidin(4)yl]-thionophosphoricacid ester of the formula ##STR21##
 5. A compound according to claim 1,wherein the compound isO-methyl-O-[6-tert.-butyl-pyrimidin(4)yl]-ethanethionophosphonic acidester of the formula ##STR22##
 6. A compound according to claim 1,wherein the compound isO-ethyl-O-[2-isopropyl-6-tert.-butyl-pyrimidin(4)yl]-methanethio-nophosphonicacid ester of the formula ##STR23##
 7. A compound according to claim 1,wherein the compound isO-methyl-O-[2-isopropyl-6-tert.-butyl-pyrimidin(4)yl]-ethanethionophosphonicacid ester of the formula ##STR24##
 8. An arthropodicidal compositioncontaining as active ingredient an arthropodicidally effective amount ofa compound according to claim 1 in admixture with a diluent.
 9. A methodof combating arthropods which comprises applying to the arthropods, orto a habitat thereof, an arthropodicidally effective amount of acompound according to claim
 1. 10. The method according to claim 9 inwhich said compoundisO,o-diethyl-O-[2-methyl-6-tert.-butyl-pyrimidin(4)yl]-thionophosphoricacid ester,O,o-dimethyl-O-[2-methyl-6-tert.-butyl-pyrimidin(4)yl]-thionophosphoricacid ester,O-methyl-O-[6-tert.-butyl-pyrimidin(4)yl]-ethanethionophosphonic acidester,O-ethyl-O-[2-isopropyl-6-tert.-butyl-pyrimidin(4)yl]-methanethionophosphonicacid ester, orO-methyl-O-[2-isopropyl-6-tert.-butyl-pyrimidin(4)yl]-ethanethionophosphonicacid ester.